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Cesium carbonate → Ethyl 4-[[5-(1,4-dioxa-8-azaspiro[4.5]decan-8-yl)-2-methyl-benzoyl]amino]-3,5-dimethyl-benzoate

HRID 239947
ノート
印刷プレビュー

反応式

HRID 239947 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]([CH3:24])=[C:6]([CH:23]=1)[C:7]([NH:9][C:10]1[C:20]([CH3:21])=[CH:19][C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:12][C:11]=1[CH3:22])=[O:8].[O:25]1[C:29]2([CH2:34][CH2:33][NH:32][CH2:31][CH2:30]2)[O:28][CH2:27][CH2:26]1.C([O-])([O-])=O.[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[O:25]1[C:29]2([CH2:34][CH2:33][N:32]([C:2]3[CH:3]=[CH:4][C:5]([CH3:24])=[C:6]([CH:23]=3)[C:7]([NH:9][C:10]3[C:20]([CH3:21])=[CH:19][C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:12][C:11]=3[CH3:22])=[O:8])[CH2:31][CH2:30]2)[O:28][CH2:27][CH2:26]1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 674351,4-Dioxa-8-azaspiro(4.5)decaneHCID 634876Binap, (A+-)-HCID 86707333Ethyl 4-[(5-bromo-2-methyl-benzoyl)amino]-3,5-dimethyl-benzoate

生成物 1

HCID 86707334Ethyl 4-[[5-(1,4-dioxa-8-azaspiro[4.5]decan-8-yl)-2-methyl-benzoyl]amino]-3,5-dimethyl-benzoate収率 36.3%

試薬・触媒・溶媒

2
HCID 167845palladium(II) acetate触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
90 °C

実験手順

To a solution of ethyl 4-[(5-bromo-2-methyl-benzoyl)amino]-3,5-dimethyl-benzoate (0.5 g, 1.28 mmol), 1,4-dioxa-8-azaspiro(4.5)decane (0.22 g, 1.54 mmol) and Cs2CO3 (1.25 g, 3.84 mmol) in THF (10 ml) is added Pd(OAc)2 (0.04 g, 0.19 mmol) followed by racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (119.7 mg, 0.19 mmol). The reaction mixture is purged with nitrogen for 5 minutes and then heated at 90° C. After 16 hours, the reaction is cooled to ambient temperature and diluted with ammonium chloride and extracted twice with EtOAc. The combined organic layers are dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting residue is purified by flash chromatography (silica gel) using 0-100% ethyl acetate in hexane to afford the title compound as a brown solid (0.21 g, 36.2%). Mass spectrum (m/z): 453.2 (M+1).

後処理

  1. customThe reaction mixture is purged with nitrogen for 5 minutes
  2. temperaturethe reaction is cooled to ambient temperature
  3. additiondiluted with ammonium chloride
  4. extractionextracted twice with EtOAc
  5. dry with materialThe combined organic layers are dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe resulting residue is purified by flash chromatography (silica gel)

出典と根拠

ORDレコード
ord-959afd17c6454dedbf835252ea1a553e
出典データセット
uspto-grants-2014_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08642768B2

反応ノート

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